Azo-dyestuffs insoluble in water and fiber dyed therewith



Patented Mar. 20, 1934 AZO-DYESTUFFS INSOLUBLE IN WATER AND DYED THEREWITH Karl Zahn and Kurt Schimmelschmidt, Franki'ort-on-the-Main, Germany, assignors to General Aniline Works, Inc.,.New York, N. Y., a corpora'tionoi' Delaware No Drawing. Application June 14, 1932, Serial No. 617,261. In Germany June 24, 1931 10 Claims.

The present invention relates to new azo-dyestuffs insoluble in water and to fiber dyed therewith; more particularly it relates to compounds of the following general formula:

O'alkyl Ho alkyl- 0 wherein X stands for a radical of the benzene series and R for a radical of the aromatic series.

We have found that new azo-dyestuffs of good fastness properties are obtainable by coupling diazo compounds of 4-amino-2.5-dialkoxy-diphenyl or of substitution products thereof with 2.3-hydroxynaphthoic acid arylides, either in substance, on the fiber or on a substratum adapted for the production of lakes, only such components being used as do not contain groups which would render the dyestuffs soluble in water and alkalies, such asthe sulfonic acid, the carboxylic acid or the hydroxy group.

The shades of thedyestuffs obtainable accord ing to the present process vary from Bordeaux to violet to blue.

The new dyestuffs are distinguished by a much better fastness to light than the dyestulfsprepared from 4-amino-diphenyl.

(a) Grounding liquor:

2.7 grams of 2'3-hydroxynaphthoyl-l-amino- 4-chloro-2.S-dimethoxy-benzene are dissolved at boiling temperature with 10 cc. of Turkey red oil of strength and 6.4 cc. of caustic soda solution of 34 B. To the boiled solution, there are added 2.7 cc. of formaldehyde solution of 30% strength. The whole is then made up with cold water to 1 liter.

(12) Developing bath A vivid, clear-violet dyeing of good fastness properties, especially of a very good fastness to light, is obtained.

The dyestuff has the following formula:

OCH:

0 OH; HO 0 O-NH Cl BIG 0 HzGO The following examples serve to ilustrate the invention, but they are notintended to limit it thereto:

(1) 50 grams of well boiled cotton yarn are treated for half-an-hour with one liter of the grounding liquor, squeezed or hydro-extracted; the wet material is then dyed in the developing bath. Thereupon, the material in a boiling soap bath and dried.

is ri nsed, soaped rates in the form of violet flakes, is filtered with suction and washed until neutral.

Dyestuffs of similar fastness properties are obtainable by replacing the diazo compound, used in the above examples, by corresponding substitution products. Instead of the coupling component mentioned in the above examples other arylides of 2.3-hydroxynaphthoic acid may be used.

The following table indicates a number of further combinations obtainable according to the present invention but is not intended to limit the invention to the dyestuffs mentioned therein:

Diazotizing component Coupling component Tints (1) 4-ainino-2.5-dimethoxydiphenyl 23-hydroxynaplithoyl-l-aminoi-chlorobenzene. Bluish violet. (2) do 2'3-hydroxynaphthoyl-l-amino-Z-methoxybcn- Dark violet.

zene. (3) do 2'3'hhydroxynaphthoyl-2-amino-3-methoxyen- Vivid violet.

t racene. (4) do 2'21; llilydroxynaphthoyl-4-amino-2.5-dimcthoxy- Dark violet.

1p eny (5) 4-amiuo-2.S-diethoxydiphenyl 23-l1ydroxynaphthoyl-l-amino-3-nitrobenzene. Reddish violet. (6) do 2'3 -hydroxynaphtlioyl-l-amino-2.5-dimethoxy- Do.

4-cl1lorobenzene. I (7) 4-amino-2.5.4-tr1metl1oxydiphenyl 2'3-hydroxynaphthoyl-1-am1no-2-meth0xyben- Blue.

, zene. i-amino-2.5-dimothoxy-4'-metliyldiphenyl do Dark violet.

23-hydroxynaphthoyl-l-aminobenrene.. Dark blue. 23-hydroxynaphthoyl-l-amino-B-mtrobenze e.. Reddish blue. 23-hydroxynaphthoyl-1-amino-4-ch1orobenzene Violetish blue. o Blackish violet.

23 hydroxynaphthoyl-l-amino-4-methy1ben- Bluish violet.

zone. 2'3 hydroxynaphthoyl-l-amino-2-methoxyben- Do.

zene. 2'3-hydroxynaphthoyl-l-aminobenzene Dark blue. 2'3 hydroxynaphthoyl-l-amino-2A-dimethoxy- Reddish violet. 3-chlorobenzcne. 17 4-amino-2.5-diinetlioxyirphenyldiphenyl 23-hydroxynaphthoyl-l-amino-3-nitr0benzene Dark violet. l8 4-a1nino-2.5-dimetl1oxY-4-benzoylamlnodiphenylfl 23-hydroxynaphthoy1-l-amino-2-methy1- Violet.

' i-chlorobenzene. (l9) 4-amino-2 5-dimethoxy-2-cl1lorodiphenyl 2'3-hydroxynaphthoyl-2-aminonaphthalene.. Bordeaux. (20) do.- 2'31;-hydroxynaphthoyl-1-ainino-2.fi-dimethoxy- Do.

enzone. (21) 4-amino-2.5-dimethoxy-3chlorodiphenyl 23'-hydroxynaphtl1oy1-l-amino-2-methyl- Violet.

. 4-metlioxybenzene. (22 do 2'3-hydroxynaphthoyl-l-aminobcnzene Bluish violet. (23 4-amino-2.5-dibutoxy-3-chlorod1pheny1 2 3-hydroxynaphtlioyl-l-amino-2-methoxyben- Currant.

' zene. 7 (24) 4-amino-2.5rdimethoxy-2'-methyldlphenyl 2'3-liydroxynaphthoyl-1amino-2.4-dimethoxy- Bordeaux.

. E-chlorobenzene. (25 4-amlno-2.5-diethoxy-3-methyld1phenyl 23-hydroxynaphthoyl- -aminonaphthelene Dark violet. (26 domino-2.5-dibutoxy-3-methyldiphcnyl 23-hydroxynaphthoyl-l-amino-2-methy1- Currant.

4-methoxybenzene. (27) 4-amino-2.5-dimethoxy-3-metl1ylsulionyldiphenyl. 2'3; -hydroxynaphthoyl-1-amino-2.5-dimethoxy- Vivid reddish violet.

GDZGDQ. (28; do 23-hydroxynaphthoyl-l-aminonephthalene. Violet. (29 4-ainino-2.5-dimethoxy3-(w-tniiuor-methyl)d1phe- 2'3; -hydroxynaphthoyl-l-amino-2.5-dimethoxy- Bordeaux.

11 enzene. (30) 4-amino-2.5-dimethoxy-34-dichlorodiphenyl 23-hydroxynaphthoyl-l-aminonaphtllalene. Violetish blue. (31) 4-amino-2.5-dimethoxy-24-dichlor0d1pheny1 2'31;-hydroxynaplithoyl-l-amino-2.fi-dimethoxy- Bordeaux.

61129118. (32) 4-amino-2.5-dimethoxy-25-dichlorodiphenyl 23ghyd goxynaphthoyl 1 amino-Z-methyM- Reddish violet.

c oro enzene. .(33) 4-a1:v1ino-2.5.4-trincrethoxy-EV-chlorodiphenyl 23-hydroxynaphthoyl-l-amino2-etl1oxybenzene Violet.

(34) 4-amino-2.5-dimethoxy-2-methyl-5-chlorodiphenyL. 23'-hydroxynaphthoyl-l-amino-3-nitrobenzene Do. (35) 4-amino-2.5-dirnethoxy-ZlH-trichlorodiplienyl 2'3 hydroxynaphthoyl 1 -amino -2- methyl Bluish Bordeaux.

4-methoxybenzene.

Since an object of the present invention is to provide dyestufis of good fastness properties, which dyestuifs are insoluble in water and alkalies, it is to be understood that the aromatic nuclei of the general formula appearing in the appended claims do not contain any substituents which are known to render organic compounds soluble in water or alkalies and to tend to depreciate the fastness of the dyestuffs to alkalies. Substituents of this kind are, for instance, the sulfonic acid, the carboxylic acid and the hydroxy group.

We claim:

l. The water-insoluble azo-dyestuffs of the following general formula:

O-alkyl HO G O-NH-R alkyl- 0 wherein X stands for a radical of the benzene series and R for a radical of the aromatic series, yielding when produced on the fiber, dyeings the shades of which vary from Bordeaux to violet to blue and being distinguished by their good fastness properties, particularly by their good fastness to light. l

2. The water-insoluble azo-dyestufis of the following general formula:

alkyl- 0 wherein X and R stand for radicals of the benzene series, yielding, when produced on the fiber, dyeings the shades of which vary from Bordeaux to violet to blue and being distinguished by their good fastness properties, particularly by their good fastness to light.

3. The water-insoluble azo-dyestuffs of the following general formula:

OCHa HO CO-NH-R wherein X and R stand for radicals of the benzene series, yielding, when produced on the fiber, dyeings the shades of which vary from Bordeaux to violet to blue and being distinguished by their good fastness properties, particularly by their good fastness to light.

4. The water-insoluble azo-dyestufis of the following general formula:

00113 HO OO-NH-R HaCO wherein R stands for a radical of the benzene series, yielding, when produced on the fiber, dyeings the shades of which vary from Bordeaux to violet to blue and being distinguished by their good fastness properties, particularly by their good fastness to light.

5. The water-insoluble azo-dyestufi of the following formula:

OGHa HO CONH QNZMQ OCHa 

